Introductory Chemical Engineering Thermodynamics, 2nd ed. J.Richard Elliott, Carl T. Lira

Book > Introductory Chemical Engineering Thermodynamics, 2nd ed. J.Richard Elliott, Carl T. Lira

Introductory Chemical Engineering Thermodynamics, 2nd ed. J.Richard Elliott, Carl T. Lira University of British Columbia BMEG 210 CONTENTS PREFACE xvii Notes to Students xviii Acknowledgments xviii ABOUT THE AUTHORS xix GLOSSARY xxi NOTATION xxv UNIT I FIRST AND SECOND LAWS 1 CHAPTER 1 BASIC CONCEPTS 3 1.1 Introduction 5 1.2 The Molecular Natur ...[Show More]

Introductory Chemical Engineering Thermodynamics, 2nd ed.

J.Richard Elliott, Carl T. Lira
University of British Columbia
BMEG 210
CONTENTS
PREFACE xvii
Notes to Students xviii
Acknowledgments xviii
ABOUT THE AUTHORS xix
GLOSSARY xxi
NOTATION xxv
UNIT I FIRST AND SECOND LAWS 1
CHAPTER 1 BASIC CONCEPTS 3
1.1 Introduction 5
1.2 The Molecular Nature of Energy, Temperature, and Pressure 6
Example 1.1 The energy derived from intermolecular potentials 12
Example 1.2 Intermolecular potentials for mixtures 14
1.3 The Molecular Nature of Entropy 15
1.4 Basic Concepts 15
1.5 Real Fluids and Tabulated Properties 22
Example 1.3 Introduction to steam tables 25
Example 1.4 Interpolation 27
Example 1.5 Double interpolation 27
Example 1.6 Double interpolation using different tables 28
Example 1.7 Double interpolation using Excel 29
Example 1.8 Quality calculations 31
Example 1.9 Constant volume cooling 32
1.6 Summary 33
1.7 Practice Problems 34
vi Contents
1.8 Homework Problems 35
CHAPTER 2 THE ENERGY BALANCE 39
2.1 Expansion/Contraction Work 40
2.2 Shaft Work 41
2.3 Work Associated with Flow 41
2.4 Lost Work versus Reversibility 42
Example 2.1 Isothermal reversible compression of an ideal gas 45
2.5 Heat Flow 46
2.6 Path Properties and State Properties 46
Example 2.2 Work as a path function 46
2.7 The Closed-System Energy Balance 48
Example 2.3 Internal energy and heat 50
2.8 The Open-System, Steady-State Balance 51
Example 2.4 Pump work for compressing H2O 55
2.9 The Complete Energy Balance 56
2.10 Internal Energy, Enthalpy, and Heat Capacities 57
Example 2.5 Enthalpy change of an ideal gas: Integrating CPig(T) 60
Example 2.6 Enthalpy of compressed liquid 60
Example 2.7 Adiabatic compression of an ideal gas in a piston/cylinder 61
2.11 Reference States 63
Example 2.8 Acetone enthalpy using various reference states 65
2.12 Kinetic and Potential Energy 66
Example 2.9 Comparing changes in kinetic energy, potential energy,

internal energy, and enthalpy 66
Example 2.10 Transformation of kinetic energy into enthalpy 67
2.13 Energy Balances for Process Equipment 68
2.14 Strategies for Solving Process Thermodynamics Problems 74
2.15 Closed and Steady-State Open Systems 75
Example 2.11 Adiabatic, reversible expansion of an ideal gas 75
Example 2.12 Continuous adiabatic, reversible compression of an ideal gas 76
Example 2.13 Continuous, isothermal, reversible compression of an ideal gas 78
Example 2.14 Heat loss from a turbine 79
2.16 Unsteady-State Open Systems 80
Example 2.15 Adiabatic expansion of an ideal gas from a leaky tank 81
Example 2.16 Adiabatically filling a tank with an ideal gas 82
Example 2.17 Adiabatic expansion of steam from a leaky tank 83
2.17 Details of Terms in the Energy Balance 85
2.18 Summary 86
2.19 Practice Problems 88
2.20 Homework Problems 90
CHAPTER 3 ENERGY BALANCES FOR COMPOSITE SYSTEMS 95
3.1 Heat Engines and Heat Pumps – The Carnot Cycle 96
Example 3.1 Analyzing heat pumps for housing 100
3.2 Distillation Columns 101
Example 3.2 Start-up for a distillation column 103
3.3 Introduction to Mixture Properties 105
3.4 Ideal Gas Mixture Properties 106
Contents vii
3.5 Mixture Properties for Ideal Solutions 106
Example 3.3 Condensation of a vapor stream 107
3.6 Energy Balance for Reacting Systems 109
Example 3.4 Stoichiometry and the reaction coordinate 110
Example 3.5 Using the reaction coordinates for simultaneous reactions 111
Example 3.6 Reactor energy balances 116
3.7 Reactions in Biological Systems 119
3.8 Summary 121
3.9 Practice Problems 122
3.10 Homework Problems 122
CHAPTER 4 ENTROPY 129
4.1 The Concept of Entropy 130
4.2 The Microscopic View of Entropy 132
Example 4.1 Entropy change and “lost work” in a gas expansion 137
Example 4.2 Stirling’s approximation in the Einstein solid 141
4.3 The Macroscopic View of Entropy 142
Example 4.3 Adiabatic, reversible expansion of steam 144
Example 4.4 A Carnot cycle based on steam 145
Example 4.5 Ideal gas entropy changes in an adiabatic, reversible expansion 149
Example 4.6 Ideal gas entropy change: Integrating CPig(T) 151
Example 4.7 Entropy generation and “lost work” 151
Example 4.8 Entropy generation in a temperature gradient 152
4.4 The Entropy Balance 153
Example 4.9 Entropy balances for steady-state composite systems 155
4.5 Internal Reversibility 158
4.6 Entropy Balances for Process Equipment 159
Example 4.10 Entropy generation by quenching 159
Example 4.11 Entropy in a heat exchanger 160
Example 4.12 Isentropic expansion in a nozzle 162
4.7 Turbine, Compressor, and Pump Efficiency 164
4.8 Visualizing Energy and Entropy Changes 165
4.9 Turbine Calculations 166
Example 4.13 Various cases of turbine outlet conditions 168
Example 4.14 Turbine efficiency calculation 171
Example 4.15 Turbine inlet calculation given efficiency and outlet 172
4.10 Pumps and Compressors 173
Example 4.16 Isothermal reversible compression of steam 173
Example 4.17 Compression of R134a using P-H chart 174
4.11 Strategies for Applying the Entropy Balance 175
4.12 Optimum Work and Heat Transfer 177
Example 4.18 Minimum heat and work of purification 180
4.13 The Irreversibility of Biological Life 181
4.14 Unsteady-State Open Systems 182
Example 4.19 Entropy change in a leaky tank 182
Example 4.20 An ideal gas leaking through a turbine (unsteady state) 183
4.15 The Entropy Balance in Brief 185
4.16 Summary 185
4.17 Practice Problems 187
viii Contents
4.18 Homework Problems 189
CHAPTER 5 THERMODYNAMICS OF PROCESSES 199
5.1 The Carnot Steam Cycle 199
5.2 The Rankine Cycle 200
Example 5.1 Rankine cycle 201
5.3 Rankine Modifications 203
Example 5.2 A Rankine cycle with reheat 204
Example 5.3 Regenerative Rankine cycle 206
5.4 Refrigeration 208
Example 5.4 Refrigeration by vapor compression cycle 209
5.5 Liquefaction 212
Example 5.5 Liquefaction of methane by the Linde process 213
5.6 Engines 214
5.7 Fluid Flow 214
5.8 Problem-Solving Strategies 214
5.9 Summary 215
5.10 Practice Problems 215
5.11 Homework Problems 216
UNIT II GENERALIZED ANALYSIS OF FLUID PROPERTIES 223
CHAPTER 6 CLASSICAL THERMODYNAMICS — 
GENERALIZATIONS FOR ANY FLUID 225
6.1 The Fundamental Property Relation 226
6.2 Derivative Relations 229
Example 6.1 Pressure dependence of H 233
Example 6.2 Entropy change with respect to T at constant P 234
Example 6.3 Entropy as a function of T and P 235
Example 6.4 Entropy change for an ideal gas 237
Example 6.5 Entropy change for a simple nonideal gas 237
Example 6.6 Accounting for T and V impacts on energy 238
Example 6.7 The relation between Helmholtz energy and internal energy 239
Example 6.8 A quantum explanation of low T heat capacity 240
Example 6.9 Volumetric dependence of CV for ideal gas 242
Example 6.10 Application of the triple product relation 243
Example 6.11 Master equation for an ideal gas 243
Example 6.12 Relating CP to CV 244
6.3 Advanced Topics 244
6.4 Summary 247
6.5 Practice Problems 248
6.6 Homework Problems 248
CHAPTER 7 ENGINEERING EQUATIONS OF STATE FOR 
PVT PROPERTIES 251
7.1 Experimental Measurements 252
7.2 Three-Parameter Corresponding States 253
7.3 Generalized Compressibility Factor Charts 256
Contents ix
Example 7.1 Application of the generalized charts 258
7.4 The Virial Equation of State 258
Example 7.2 Application of the virial equation 259
7.5 Cubic Equations of State 260
7.6 Solving the Cubic Equation of State for Z 263
Example 7.3 Peng-Robinson solution by hand calculation 266
Example 7.4 The Peng-Robinson equation for molar volume 266
Example 7.5 Application of the Peng-Robinson equation 268
7.7 Implications of Real Fluid Behavior 269
Example 7.6 Derivatives of the Peng-Robinson equation 269
7.8 Matching the Critical Point 270
Example 7.7 Critical parameters for the van der Waals equation 271
7.9 The Molecular Basis of Equations of State: Concepts and Notation 271
Example 7.8 Estimating molecular size 273
Example 7.9 Characterizing molecular interactions 275
7.10 The Molecular Basis of Equations of State: Molecular Simulation 276
Example 7.10 Computing molecular collisions in 2D 279
Example 7.11 Equations of state from trends in molecular simulations 281
7.11 The Molecular Basis of Equations of State: Analytical Theories 282
Example 7.12 Deriving your own equation of state 288
7.12 Summary 289
7.13 Practice Problems 290
7.14 Homework Problems 291
CHAPTER 8 DEPARTURE FUNCTIONS 301
8.1 The Departure Function Pathway 302
8.2 Internal Energy Departure Function 304
Example 8.1 Internal energy departure from the van der Waals equation 306
8.3 Entropy Departure Function 307
8.4 Other Departure Functions 308
8.5 Summary of Density-Dependent Formulas 308
8.6 Pressure-Dependent Formulas 309
8.7 Implementation of Departure Formulas 310
Example 8.2 Real entropy in a combustion engine 310
Example 8.3 Compression of methane using the virial equation 312
Example 8.4 Computing enthalpy and entropy departures from the

Peng-Robinson equation 314
Example 8.5 Enthalpy departure for the Peng-Robinson equation 316
Example 8.6 Gibbs departure for the Peng-Robinson equation 317
Example 8.7 U and S departure for the Peng-Robinson equation 317
8.8 Reference States 318
Example 8.8 Enthalpy and entropy from the Peng-Robinson equation 320
Example 8.9 Liquefaction revisited 320
Example 8.10 Adiabatically filling a tank with propane 322
8.9 Generalized Charts for the Enthalpy Departure 323
8.10 Summary 323
8.11 Practice Problems 325
8.12 Homework Problems 326